Poly (N-isopropylacrylamide) microgel based assemblies for organic dye removal from water: microgel diameter effects

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the “nature” of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake—the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model.     

Oxidation of azo dye Orange II with hydrogen peroxide catalyzed by 5,10,15,20-tetrakis[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II)tetraiodide in aqueous solution

The catalytic oxidation of the azo dye Orange II by hydrogen peroxide in aqueous solution has been investigated using 5,10,15,20-tetrakis-[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II) tetra iodide 1as catalyst. The oxidation reaction was followed by recording the UV–vis spectra of the reaction mixture with time at λ_max = 485 nm. The factors that may influence the oxidation of Orange II, such as the effect of reaction temperature, concentration of catalyst, hydrogen peroxide and orange II have been studied. The results of total organic carbon analysis showed 52% of dye mineralization under mild reaction conditions. Residual organic compounds in the reaction mixture were identified by using Gas chromatography-mass spectrometry. The decolorization rate and mineralization of the dye has been found to increase with increase of catalyst concentration and reaction temperature. The rate of dye oxidation decreased with increasing the concentration of dye, H₂O₂ and at higher pH than 9. Radical scavenging measurement indicated that decolorization of Orange II by H₂O₂/cobalt (II) porphyrin complex 1 involved the formation of hydroxyl radicals as the active species.     

Solvothermal synthesis of WO3/TiO2/carbon fiber composite photocatalysts for enhanced performance under sunlight illumination

Carbon fiber (CF)‐based WO₃/TiO₂ composite catalysts (WO₃/TiO₂/CF) were successfully synthesized by solvothermal method. The catalysts were characterized by XPS, SEM, BET, XRD, FTIR, Raman and UV–Vis. The analyses confirmed the WO₃/TiO₂ nanoparticles with high crystallinity deposited on the carbon structure. The photocatalytic degradation of Orange II azo dye under UV and sunlight illumination with the synthesized catalyst was explored. The composite catalyst displayed high performance (85%) for Orange II degradation while that of for WO₃/TiO₂ was found as 76%. The effects of CF amount, solution pH, initial dye concentration and catalyst dose on photocatalytic performance were studied. It was found that the degradation efficiency increased from 68% to 90% with the increasing CF amount from 3 wt% to 5 wt%, while the further increase in CF amount (7–10 wt%) decreased the photodegradation due to the blocking the active sites of WO₃/TiO₂. The enhanced photocatalytic efficiency was mainly attributed to the electrical properties of the CF and reduced bandgap.     

Application of microgels as polymer supports for organic synthesis: preparation of a small phthalide library,a scavenger,and a borohydride reagent

Microgel polymers containing a series of functional groups have been prepared. These microgels were composed of cross-linked poly(styrene) and were prepared by radical polymerization in solution. The microgel polymers exhibit good solubility in an array of different organic solvents, and in addition, they can be efficiently precipitated by the addition of methanol and isolated by filtration. A nine-member phthalide library was synthesized using an aminomethyl-functionalized microgel 5. To further demonstrate the versatility of these microgel polymers, tris(2-aminoethyl)amino microgel 11 was examined as a scavenger reagent to remove unreacted isocyanate after a urea synthesis. Finally, a microgel-supported ammonium borohydride reagent 14 was successfully prepared and used as a reducing agent. Notable features of these microgels are that in all applications the progress of the reaction could be monitored by standard NMR techniques and their preparation is performed using common glassware and techniques found in all organic laboratories.     

Aloe vera–eluting collagen I microgels: physicochemical characterization and in vitro biological performance

Microgels absorb and retain high amounts of solvents, especially water. Because of their size, and association, the release kinetics of active molecules from microgels is easier to control than in hydrogels. Collagen I is one of the most extensively investigated biomaterials, although the key process parameters to produce microgels must be understood well before they can be used in veterinary and human medicine. Emulsification-gelation is widely used to obtain microgels because of its ease of handling and high yields. The concentration of the biomaterial and the homogenization method are among the critical parameters in this method. In this work, we produced cytocompatible collagen I microgels by emulsification-gelation and evaluated the effect of three different concentrations and homogenization methods on their physicochemical, mechanical, and biological properties. As proof of concept, microgels were loaded with an Aloe vera extract and the loading efficiency and the polyphenol release kinetics, as well as their properties assessed. When the same homogenization method (e.g. magnetic stirring) was used, the size of the microgels decreased with an increase of collagen I concentration, and the size distribution increased. In addition, the size and size distribution of microgels prepared with the same collagen I concentration were smaller when produced by high-energy homogenization methods (shear stress and ultrasound) than with a low-energy one (magnetic stirring). Collagen I concentration and the homogenization method also influenced the zeta-potential, the enzymatic degradation, and the encapsulation efficiency of the microgels. Overall, we show that the size of these microgels can be fine-tuned by the collagen I concentration and the homogenization method. Moreover, the integration of microgels of different sizes into the same carrier platform will pave the way for the combination of active compounds with different release kinetics.     

Novel self-assembling system based on resorcinarene and cationic surfactant

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties.     

Complexation and flotation of nonferrous metal ions from alkaline solutions with N-acyl-N′-(p-toluenesulfonyl)hydrazines

Surfactant properties and complexation conditions of Cu(II), Co(II), Ni(II), Zn(II), and Cd(II) ions in alkaline media with N-acyl-N′-(p-toluenesulfonyl)hydrazines, which enable their use in ion flotation processes, were studied. The efficiency of the compounds under study as collectors in aftertreatment of alkaline wastewater to remove milligram amounts of Cu(II) and other metals by ion flotation was demonstrated.     

Effects of Hofmeister anions on the flocculation behavior of temperature-responsive poly(N-isopropylacrylamide) microgels

Effects of some sodium salts (NaCl, NaClO₃, and NaSCN) in the Hofmeister series on deswelling and temperature-induced aggregation behavior of microgels of poly(N-isopropylacrylamide) (PNIPAAM) and PNIPAAM-co-PAA with attached poly(acrylic acid) moieties were investigated with the aid of turbidimetry and dynamic light scattering. Addition of salt in the concentration range 0.1–0.5?M generated aggregation of the PNIPAAM microgel particles at elevated temperatures, but it was no distinct difference between chaotropic and kosmotropic anions. In contrast, the flocculation behavior at high temperatures for PNIPAAM-co-PAA revealed a prominent influence of salinity and type of anion on the formation of aggregates. The aggregation transition was shifted to the highest temperature for the most chaotropic anion (SCN^?), and the aggregation transition at the same salt concentration is consistent with the typical Hofmeister series. The turbidity results from the PNIPAAM-co-PAA microgels disclosed a two-step transition for the considered anions, and both a low and high temperature change in the turbidity data was observed. The high-temperature transition followed the Hofmeister series.     

A new fast swelling poly[DAPB-co-DMAAm-co-AASS] superabsorbent hydrogel for removal of anionic dyes from water

The objective of this research is to utilize a new poly[N,N-diallyl pyrrolidinium bromide-co-N,Ndimethyl acrylamide-co-acrylic acid sodium salt]superabsorbent hydrogel（SAH）for the removal of two anionic dyes,e.g.,Reactive Red 5B（RR5B）and Reactive Orange M2R（ROM2R）,from water.The SAH was characterized by swelling in water,FTIR,TGA and SEM.The SAH DDA6showed good swelling property and thermal stability.We have also investigated the parameters affecting dye adsorption such as pH,adsorbent dose,adsorption rate and initial dye concentration.The experimental data were also analyzed by applying the well known Langmuir and Freundlich isotherm models.     

Chromonic liquid crystals formed by CI Acid Red 266 and related structures

Chromonic liquid crystals are currently receiving increased attention because they have applications in a wide range of products. In this study, we have compared the chromonic mesophase behaviour of four azo dyes with similar chemical structures. Our objective is to determine if there is an obvious link between mesophase formation and dye chemical structure. Orange G does not form mesophases over the concentration range examined (saturated solution > ~20–30 wt%). The other three compounds all form nematic (N) and hexagonal (H) mesophases, but over very different concentration ranges. X-ray diffraction shows that the ordered Edicol Sunset Yellow (ESY) aggregates present in the mesophases have a single molecule cross section, while those of CI Acid Red have a cross section equivalent to six to eight molecules, probably organised in a ‘water-filled pipes’ structure. NMR quadrupole splittings of ²H₂O demonstrate that water binding to the aggregates is similar to that found for surfactant lyotropic mesophases. The sodium (²³Na) quadrupole splittings for Orange II and CI Acid Red are similar to the values found for surfactant hexagonal phases, suggesting that most sodium ions are ‘bound’ to the aggregates. This is unlike the behaviour of ESY where only one of the two sodium ions is bound.     

The impact of the cononsolvency effect on poly (N-isopropylacrylamide) based microgels at interfaces

The paper addresses the effect of solid interfaces on the cononsolvency effect for poly(N-iso propylacrylamide) based microgels containing different contents of the co-monomer allyl acetic acid (AAA). The cononsolvency effect is studied by dynamic light scattering (DLS) in solution and with atomic force microscopy (AFM) at surfaces against different mixtures of water and organic solvent (ethanol, iso-propanol, and tetrahydrofuran). For the studies at interfaces, the microgels are spin coated on silicon wafers that are precoated with poly(allylamine hydrochloride) (PAH). The minimum in particle volume due to cononsolvency shows a pronounced shift from 10–20 % of organic solvent to 40–50 % after deposition at the Si/PAH wafer. The strong shift indicates an increase of water to organic solvent ratio within the gel at the surface with respect to the bulk solution. In order to understand the increase of water to organic solvent ratio, shrinking/reswelling AFM experiments for different spin-coating conditions and under ambient conditions are carried out. Spin coating from water instead from different solvent mixtures has no effect on the cononsolvency. In ambient conditions, the cononsolvency effect disappears     

J Aggregation of Thiacarbocyanine in Aqueous Gelatin Solutions

The aggregation processes of 3,3′-disulfopropyl-4,4′,5,5′-dibenzo-9-ethylthiacarbocyanine betaine were studied in aqueous gelatin solutions. Gelatin molecules were shown to favor the formation of J aggregates from dye dimers according to the block mechanism. Acidic gelatins much stronger favor J aggregation of the dye than alkaline and, especially, modified gelatins. High contents of microgels and high-molecular-mass fractions in gelatin retard the formation of long-wavelength aggregates.     

Photodegradation of orange II dye using p-n junction NiO/TiO2 composite,and assessment of its biological activities

The chemical reduction method was used to synthesize nickel oxide particles (NiO) and NiO supported on titanium dioxide (NiO/TiO₂ nanocomposite). The composites were characterized through scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The morphological investigation showed that pseudocubic NiO are present in dispersed as well as agglomerated forms. Whereas NiO particles (<200 nm) are evenly deposited over the surface of TiO₂ in NiO/TiO₂ composite. The formation of NiO and NiO/TiO₂ was also verified by XRD analysis. The synthesized NiO and NiO/TiO₂ were used as photocatalysts for the degradation of Orange II (OII) dye. According to the degradation investigation, both NiO and NiO/TiO₂ composite degraded OII dye more efficiently when exposed to UV light. The results indicated that NiO degraded 93% and NiO/TiO₂ composites degraded approximately 96% of OII dye within 30 min. Both photocatalysts are highly sustainable and have significant OII dye degradation recyclability. Moreover, NiO and NiO/TiO₂ exhibited promising bioactivities (antioxidant activity of 80%) against the pathogenic bacteria Citrobacter and Providencia, which is comparable with the standard ascorbic acid (88%).     

Decolorization and partial degradation of selected azo dyes by methanogenic sludge

The toxicity potential and decolorization of three acid azo dyes (Acid Orange 6, Acid Orange 7, and Acid Orange 52) by methanogenic granular sludge from an anaerobic expanded granular sludge bed reactor was assayed. Complete bioreduction was found for all three azo dyes. Sulfanilic acid and 4-aminoresorcinol were detected from the decolorization of Acid Orange 6, sulfanilic acid and 1-amino-2-naphtol were detected from the reduction of Acid Orange 7, and sulfanilic acid and N,N-dimethyl-1,4-phenylenediamine (DMP) were found to be intermediates of Acid Orange 52 degradation. Sulfanilic acid and 1-amino-2-naphtol were persistent in the anaerobic conditions, whereas 4-aminoresorcinol was completely mineralized by anaerobic sludge and DMP was transformed into 1,4-phenylenediamine. Enrichment cultures obtained via consecutive passages on basal medium with only azo dye as a carbon and an energy source seemed to be morphologically heterogeneous. Baculiform and coccus cells were found when viewed under a light microscope. Cocci were joined in chains. Because anaerobic sludge contains sulfate-reducing bacteria and therefore may generate sulfide, azo dyes were tested for chemical decolorization by sulfide to compare rates of chemical and biologic reduction.     

Remarkably high catalytic activity of the Ru(III)(edta)/H2O2 system towards degradation of the azo-dye Orange II

The Ru(III)(edta)/H(2)O(2) system (edta(4-) = ethylenediaminetretaacetate) was found to degrade the azo-dye Orange II at remarkably high efficiency under ambient conditions. Catalytic degradation of the dye was studied by using rapid-scan spectrophotometry as a function of [H(2)O(2)], [Orange II] and pH. Spectral analyses and kinetic data point towards a catalytic pathway involving the rapid formation of [Ru(III)(edta)(OOH)](2-) followed by the immediate subsequent degradation of Orange II prior to the conversion of [Ru(III)(edta)(OOH)](2-) to [Ru(IV)(edta)(OH)](-) and [Ru(V)(edta)(O)](-)via homolysis and heterolysis of the O-O bond, respectively. The higher oxidation state Ru(IV) and Ru(V) complexes react three orders of magnitude slower with Orange II than the Ru(III)-hydroperoxo complex. In comparison to biological oxygen transfer reactions, the Ru(edta) complexes show the reactivity order Compound 0 ? Compounds I and II.     

Reversible crosslinking in cellulose. VII. Memory effect of the crosslinking medium in the dyeing of crosslinked cotton

Cellulose β-mercaptoethylaminocarboxylate made from unmercerized cotton was partially oxidized in various solvents of different swelling power followed by treatment with excess methyl iodide to yield partially disulfide-crosslinked cotton samples of about the same degrees of crosslinking containing sulfonium groups of about the same contents. The effect of the solvent in crosslinking on the equilibrium and kinetics of dyeing with three dyes (Orange II, Direct Scarlet B, and Direct Sky Blue A) of different molecular size was investigated. The 1:1 ionic bonding was observed at equilibrium between sulfonic acid groups in dye molecules and sulfonium groups in modified cottons in cases of Orange II and Direct Scarlet B. The equilibrium uptake of the largest dye, Direct Sky Blue A, was much influenced by the solvent used in crosslinking; the higher the degree of swelling in crosslinking, the larger the equilibrium uptake. The diffusion rate of Direct Scarlet B was much affected by the solvent used; the higher the degree of swelling, the higher the diffusion rate. The pore structure of the crosslinked cotton was discussed. The crosslinked cotton seemed to have a “memory” of the state at the time of crosslinking and to have a tendency to come back close to that state when placed in a dye bath.     

Über die rolle der Aminogruppen der Faser für die Sorption von anionischen farbstoffen: Versuche mit Amino- und Hydroxypolypropylen 15. Mitteilung über textilchemische Untersuchungen [1]

(1) Three anionic mono azo dyes (Orange I, Orange II and Orange 8) and a 1:2 metal complex dye (Cibalan Grey BL) are dyed onto aminopolypropylene. With all the dyes, a Langmuir isotherm with a stoichiometric relation between the dye adsorbed and the concentration of amino groups on the substrate is obtained.     

A spectral approach to determine location and orientation of azo dyes within surfactant aggregates

The UV–vis absorption properties of azo dyes are known to exhibit a variation with the polarity and acidity of the dye environment. The spectral properties of a series of anionic azo dyes were characterized to further probe the interaction of these dyes with two types of surfactant aggregates: (1) the spherical micelles formed in aqueous solution by alkyltrimethylammonium bromide (C_nTAB) surfactants with n = 10–16 and (2) the unilamellar vesicles spontaneously formed in water from binary mixtures of the oppositely-charged double-tailed surfactants cationic didodecyldimethylammonium bromide (DDAB) and anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT). The observed dye spectra reflect the solvatochromic behavior of the dyes and suggest the location and orientation of the dye within the surfactant aggregates. Deconvolution of the overall spectra into sums of Gaussian curves more readily displays any contributions of tautomeric forms of the azo dyes resulting from intramolecular hydrogen bonding. The rich variation in UV/vis absorption properties of these anionic azo dyes supports their use as sensitive tools to explore the nanostructures of surfactant aggregates.     

In Silico and in Vitro Physicochemical Screening of Rigidoporus sp. Crude Laccase-assisted Decolorization of Synthetic Dyes—Approaches for a Cost-effective Enzyme-based Remediation Methodology

The objective of this paper is to compare in silico data with wet lab physicochemical properties of crude laccase enzyme isolated from Rigidoporus sp. using wheat bran as solid substrate support towards dye decolorization. Molecular docking analysis of selected nine textile and non-textile dyes were performed using laccase from Rigidoporus lignosus as reference protein. Enzyme-based remediation methodology using crude enzyme enriched from solid state fermentation was applied to screen the effect of four influencing variables such as pH, temperature, dye concentration, and incubation time toward dye decolorization. The extracellular crude enzyme decolorized 69.8 % Acid Blue 113, 45.07 % Reactive Blue 19, 36.61 % Reactive Orange 122, 30.55 % Acid Red 88, 24.59 % Direct Blue 14, 18.48 % Reactive Black B, 16.49 % Reactive Blue RGB, and 11.66 % Acid Blue 9 at 100 mg/l dye concentration at their optimal pH at room temperature under static and dark conditions after 1 h of incubation without addition of any externally added mediators. Our wet lab studies approach, barring other factors, validate in silico for screening and ranking textile dyes based on their proximity to the T1 site. We are reporting for the first time a combinatorial approach involving in silico methods and wet lab-based crude laccase-mediated dye decolorization without any external mediators.     

Novel D-π-A type II organic sensitizers for dye sensitized solar cells

Four organic donor-π-conjugated-acceptor (D-π-A) type II dyes with different thiophene linkers are reported for dye sensitized solar cells (DSSCs). For the first time, a donor (triphenylamine) was introduced in type II sensitizers, and 2-hydroxybenzonitrile as acceptor/anchoring moiety was covalently linked TiO₂ particles. The dye LS203 in this series gives the best solar energy conversion efficiency of 3.4%, with J_sc = 7.4 mA cm⁻², V_oc = 0.67 V, FF = 0.69, the maximum IPCE value reaches 66.9%.